Cyanoalkylated polyoxyalkylene polyamines

ABSTRACT

Cyanoalkylated polyoxyalkylene polyamines of the formula WHEREIN A is a cyano-lower-alkyl radical or hydrogen provided at least one A is a cyano-lower-alkyl radical are useful as coupling agents for polymer formation and as curing agents in sprayed polyurea coatings.

United States Patent Rowton 1 May 30, 1972 [541 CYANOALKYLATED 3,364,2481/1968 Miller, Jr. et al ..260/465.5 R POLYOXYALKYLENE POLYAIVIINES3,544,615 12/1970 Poppelsdorf ..260/465.5 R X [72] Inventor: Richard LeeRowton, Austin, Tex. OTHER PUBLICATIONS [73] Assignee: JeffersonChemical Company, Inc., Degering, An Outline of Organic NitrogenCompounds,"

Houston, Tex. 1945, pp. 701- 702. [22] Filed: 1969 PrimaryExaminer-Joseph P. Brust [2]] Appl No 352,487 Attorney-Carl G. Ries,John R Kirk, Jr. and H. G. Jackson [57] ABSTRACT [52] U.S. Cl...260/465.5 R, 260/292 TN, 260/77.5 C,

260/775 AQ 260/584 Cyanoalkylated polyoxyalkylene polyammes of theformula [51] Int. Cl ..C07c 121/42 2 )n IC1 NII-AI..1 [58] Field ofSearch ..260/465.5 R y w W V wherein A is a cyano-lower-alkyl radical orhydrogen pro- [56] References Cited vided at least one A is acyano-lower-alkyl radical are useful UNITED STATES PATENTS as couplingagents for polymer formation and as curing agents in sprayed polyureacoatings. 3,236,895 2/1966 Lee et al ..260/584 B 3,337,606 8/1967 Floyd..260/465.5 R 9 Claims, No Drawings CYANOALKYLATED POLYOXYALKYLENEPOLYAMINES CROSS REFERENCE TO RELATED APPLICATION BACKGROUND OF THEINVENTION 1. Field of the Invention This invention pertains to the fieldof new organic chemicals.

ZJDescription of the Prior Art The compounds of this invention areprepared by the cyanoalkylation of polyoxyalkylene polyamines.Polyoxyalkylene polyamines useful in preparing the compounds of myinvention are disclosed in Lees U.S. Pat. No. 3,236,895 (1966) and inYeakeys co-pending US. Patent Application I Ser. No. 602,167 filed Dec.16, 1966. In spray polyurea coatings, a short delay in curing time isnecessary. Polyoxyalkylene polyamines react almost instantaneously withisocyanates; therefore, these amines cannot be used in spray coatings ofpolyureas or polyurethanes utilizing an isocyanate orisocyanate-prepolymer because of the immediate gel or hardening of thepolyurea when the amine is added. By using the cyanoalkylatedpolyoxyalkylene polyamines of my invention, gel times are such that goodmixing of the isocyanate and amine can be obtained and the sprayedmaterial has time enough to adhere and level before gellation of thepolyurea coating occurs.

SUMMARY OF THE INVENTION My invention is compounds of the formula R'(OClIzCH)nCHCH-NH-A]m l l y where R is the nucleus of anoxyalkylation-susceptible aliphatic polyhydric alcohol containing 2 l2carbon atoms and 2 8 hydroxyl groups, A is hydrogen, or a cyano-lower--alkyl radical having one or two carbon atoms between the nitrogen andcyano radical provided at least one A is a cyanolower-alkyl radical, Zis an alkyl group containing I 18 carbon atoms, X and Y are hydrogen orZ, n has an average value of 0 50 and m is 2 8. R is saturated andconsists of carbon and hydrogen. The methyl and ethyl alkyl groups of Amay be substituted with lower alkyl groups. The amines of my inventionare useful as coupling agents for polymer formation. The amines of myinvention are particularly useful as curing agents in polyurea coatings,for example, sprayed polyurea coatings.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The cyanoalkylatedpolyoxyalkylene polyamines of my invention are prepared frompolyoxyalkylene polyamines. Polyoxypropylene diamines having a molecularweight of about 190 to about 2,000 are useful in preparing thepolyoxypropylene diamines of this invention and polyoxypropylenediamines having a molecular weight of about 190 to about 1,000 arepreferred starting materials for the compounds of my invention. Theseamines have the general formula $11; (131k) I IzNC IICII: O CII;-CII NHwhere y is a number from about 2 to about 16. Polyoxypropylene triaminesof the formula I 1N ll:

on.) I O CH:L lI INH? where x y z is an average of 5.3 are alsousefulstarting materials for the compounds of my invention. Examples land ll, infra, illustrate typical preparations of the compounds of myinvention.

EXAMPLE I To a solution of I g. (1 mol) of polyoxypropylene diamine of190 molecular weight and 200 ml. of water was added dropwise withstirring 106 g. (2 mols) of acrylonitrile over a 30-minute period. Themixture exothermed, but the temperature was not allowed to go over 50 C.After standing overnight, volatile material was removed under fullvacuum at temperatures up to C. Recovery of the reactants was 100percent. The product, a nearly colorless and somewhat viscous liquid,had the following analysis in milliequivalents per gram:

Amine Meq/g. Primary 0. l 9 Secondary 6.69 Tertiary 0.02

Total 6.90

Thus, the N,N-disubstituted product of the formula was produced in 97percent yield. The remaining cyanoethy- EXAMPLE II To 400 g. (1 mol) ofnitrogen-blanketed polyoxypropylene diamine of 400 molecular weight wasadded dropwise'with stirring 163 g. (2 mols) of 70 percent aqueousglycolonitrile. The mixture exoth'ermed and 'the reaction was allowed toproceed at 40 50 C. After the nitrile addition 'was complete, thereaction mixture was allowed to stand for several hours at ambienttemperatures. A 100 percent excess of calcium hydroxide was added toneutralize the 0.5 percent phosphoric acid present in the nitrile. Alterstanding a few more hours, water was stripped out at up to C. under fullvacuum. Filter aid was added and the mixture filtered. A light brownliquid was obtained which had the following analysis:

Amine Meq/g. Primary 0.03 Secondary 3.92 Tertiary 0. l 6

Total 4.l l

The remaining cyanomethylated compounds of my invention are prepared inthe same manner and comparable results are obtained when otherpolyoxyalkylene polyamines are reacted with glycolonitrile or.lactonitrile. The reactions preparing the compounds of my invention areselective in that N,N'-disubstitution takes place. If completesubstitution of the amine hydrogens occurred, the products would not besatisfactory for use as curing agents for polyurethanes.

The following tables illustrate the utility of the compounds of myinvention as curing agents for polyurethanes. Gel times are reported inseconds. The following abbreviations are used in the tables:

Amines .IEFFAMINE D-X Polyoxypropylene Diamine of x Molecular WeightJEFFAMINE T-403 Polyoxypropylene Triamine of 450 Molecular Weight AmineSufiixes triamjnes.

CE I N-(Z-Cyanoethyl) The data in Table III illustrates theimpracticality of using S sy- 2 Y Y I aliphatic primary amines as curingagents for polyureas yanoet y because of the extremely short gel times.

TABLE III Reactants Solvent Amount, Gel time, Isooyanate componentsAmine components Name percent sec.

'IDI Jefiamine D-400 Methyl ethyl ketone 65 Immediat LMDI IefiamineD-400 do 5 D0, PAI "d 65 Do. HMDL- do. 50 1. HMDI Jefiamlnc D- 3 50Immediate. LMDI/PPG 600 (6/1) .Tefiamme D-400 55 p CM N-(Cyanomethyl)Example III illustrates a polyurea spray coating using the I Y ycyanoethylated 400 molecular weight polyoxypropylene socyana es TDIToluene Diisocyanate, 80:20 dlamme of my Invention lsomer Mixture LMDILiquid Diphenylmethane Diisocyanate HMDI Hydrogenated MDI EXAMPLE IIIPAI Polymeric Aromatic Isocyanate 2O Polyols Component A a 50:50 weightpercent blend of liquid PPG Polypropylene Glycol ofx diphenylmethanediisocyanate and hydrogenated liquid Molecular Weight The abbreviationsfor the component compositions of the polyureas are illustrated asfollows: 3:1 LMDI:TDI/PPG80O (2/1) is a mixture of three isocyanateequivalents of LMDI and one equivalent of a TDI/PPG800 prepolymer, thelatter being made from two equivalents of TDI and one equivalent ofPPG-800. In each of the Tables, a theoretical equivalent amount of theamine component was added to the isocyanate component contained in asmall cup while the mixture was stirred as rapidly as possible with apaddle-type stirrer. After 10 seconds of stirring, a portion of themixture was poured onto a pan and spread out with a spatula to form afilm. Gel time in the cup was noted and recorded and the physical natureof the film was recorded If a solvent was used, it was distributedbetween the two components so that each component was of low viscosity.Films containing solvent were dried in an oven at 80 C. beforeevaluation. Those mixtures marked with an asterisk did not gel, butthickened to a fairly stiff consistency in the time noted.

The data in Table II illustrate the practical gel times obtained usingcyanoethylated polyoxypropylene diamines and diphenylmethanediisocyanate containing 7.3 meq. isocyanate per gram and Component B thecyanoethylated 400 molecular weight polyoxypropylene diamine containing4.4 meq./g. of amino hydrogen and diluted with 5 percent of its weightof methylene chloride were pumped through a twocomponent airless Gusmerspray rig at a Component B/Component A ratio of 1.67/1. In the sprayrig, the two accurately 0 metered streams of reactants were broughttogether in a small chamber, rapidly mixed, and ejected through a spraynozzle. The spray was applied to a rigid urethane foam substrate,whereon it gelled within a few seconds. The sprayed film thus protectsthe foam from abrasion and degradation. Using this technique, a sprayedfilm of any thickness can be applied to a surface. These sprayedpolyurethane coatings are useful protective coatings which can be usedin any field where protective coatings are desirable.

Example IV illustrates the utility of the compounds of my invention ascoupling agents for polymers. Example IV is the preparation of aurethane latex using bis-cyanoethylated polyoxypropylene diamine ofmolecular weight 190 as a coupling agent.

TABLE 1 Reactants Solvent Gel Amount, time, Isocyanate components Aminecomponents Name percent sec. Nature of film LMDI BCE/JEFFAMINETM D400Methyl ethyl ketone-.. 60 15 Soft, d pliab1e Do CE/JEFFAMINE D400-.- do65 17 Stifi and strong, PAI BCEIJEFFAMINE D-400 .-d0- 65 26 Fairl stifiand str HMDI ..do l N n 60 Soft and fairly strong.

Do CE/JE FAMINE D-400 .do..- '30 Slightl Stilt. Fairly resi lent.LMDI/PPG-800 (2/1) BCE/JEFFAMINE D400-- Toluene 50 15 Soft. Strong andelastic, LMDI/PPG-sotl (6/1) CE/JEFFAM NE D400 Methy e hyl ket 65 18Fairliy stllli. Fair strength an resi ience. lAI/PPG-SOO (15/1) /JE FAM1 -400.- 12 Soft and pliable. 1 :2 HMDIzLMDI/PP G-8U0 (ti/1)-...GE/JEFFAMINE D-400. 4 Slighdtlyl stitllligood strength on e as o y. 1:1HMDIzLMDI/PP G-IODO (t/1) .110 15 Soft and elastic. 1:2 PAI:TDI/PP G-GOO(2/ BCE/J EFFAMIN E Methyl 15 Soft and pliable.

1:1 LMDI:LMDI/PPG800 (2/1). BCE/ EFFAM NETM D- Toluene 50 12 Fairliystiig. Fair strength an res once. 1:1:2 HMDLPALTDI/PP (3-600 (2/1)CE/JEFFAMINE D-230 Methylene chlonde 8 o. LMDI/PP (3-800 (2/1)TCE/JEFFAMINE T- Methyl ethyl ketonom 65 7 Soft and elastic.HMDI/PPG-SOO (2/1) CE/JEFFAMINE T403. Toluene 1 5-6 Do. 2:1 HMDI;TDI/PPGBCE/JEFFAMINE T-40 None l5 Fairly stlfl. Fair strength and resilience.

i TABLE 11 Reactants Solvent Gel Amount e, Isocyanate components Aminecomponents N ame percent sec. Nature of film BCM/JEFFAMINETM 13-400 30Soft and elastic. BCM/JEFFAMINE D-400. 10 Fairlg stiff. Fair strengthand res ience. CM/JEFFAMINE D-400. Methyl ethyl ketone. 65 1 330 Stiffand strong. CM/JEFFAMINE D400" do-.-- 65 1% Do. BCM/JEFFAMINE D-400Methylene chloride 35 20 Soft and pliable. MD CM/JEFFAMINE 10400.-..None Somewhat stlfi. Fair resilience. 8:1 LMDI:TDI[PPG8OO (2/1)BCM/JEFFAMINE D-400- do 15 Soft and pliable. 1:2 PAIzTDI/PP G400 (2/1).CM/JEFFAMINE D-230 Methylene ch10 46 Soft but strong.

l Min.

3 666,7 8 8 5 6 EXAMPLE IV 5. A compound according to claim 2 of theformula A prepolymer was made by heating for four hours at 80 CH 90 C. amixture of polyoxypropylene glycol of 800 molecular a weight (PPG800)and a 100 percent molar excess of 5 2 "oqcnrcn" :NHCIIZCHZCN toluenediisocyanate (TDI). Seven grams of surfactant dism solved in 93 g. ofwater was added to a stirred solution of 140 I g. of the urethaneprepolymer and 30 g. of toluene. The result- L CH2 OCm bu "NHCHZOHWN ingemulsion was passed through a homogenizer and then an CU! aqueoussolution containing the cyanoethylated compound of NHC 11 CH CN Examplel, in an amount equivalent to the NCO groups, was added with gentlestirring. The final emulsion contained 50 wherein z is an average ofpercent total solids. The resulting latex had excellent 6 A compoundaccording to l i 1 h i h cyanomechanical stability. Upon drying, a softrubber was obtained. radical i cyanomethyL I claim: 1 5 7. A compoundaccording to claim 6 of the formula 1. A compound of the formula 20wherein R is the nucleus of an oxyalkylation-susceptible saturatedpolyhydric alcohol containing 2l2 carbon atoms and g 1 28 hydroxylgroups and R consists of carbon and hydrogen, wherein y is a number f 2to about A is a y y radical Z is an alkyl group containing 8. A compoundaccording to claim 7 of the formula l-l 8 carbon atoms, X and Y arehydrogen or Z, n has an average value of050 and m is 28. CH3 CH CH 2. Acompound according to claim 1 wherein the cyano- NC lower-alkyl radicalis cyanoethyl.

A compound according t0 claim 2 Ofthe formula 9. A compound according toclaim 6 of the formula (IJII; (EH3) CH3 NCClLOILNIIICI CIT. 0 ClLClI,NlILH LIIzCN CH2 NHCHCN I l C Ha wheremyisanumber from 2to about 16.(how )NHCHzCN 4. A compound according to claim 2 of the formula

2. A compound according to claim 1 wherein the cyano-lower-alkyl radicalis cyanoethyl.
 3. A compound according to claim 2 of the formula
 4. Acompound according to claim 2 of the formula
 5. A compound according toclaim 2 of the formula
 6. A compound according to claim 1 wherein thecyano-lower-alkyl radical is cyanomethyl.
 7. A compound according toclaim 6 of the formula
 8. A compound according to claim 7 of the formula9. A compound according to claim 6 of the formula